Color developing with a 4-sulfo naphthamide base

ABSTRACT

THIS APPLICATION DESCRIBES A COMPOUND OF THE FORMULA:   1-(R1-O-),2-(R2-N(-R3)-CO-),4-(HO3S-)NAPHTHALENE   WHEREIN R1 IS SELECTED FROM AN ALKYL, ARALKYL, ALKARYL, ACYL AND A SUBSTITUTED ACYL GROUP AND R2 AND R3 ARE EACH SELECTED FROM A HYDROGEN ATOM AND AN ALKYL, ARALKYL, ALKARYL, ARYL AND A SUBSTITUTED ARYL GROUP. COMPOUNDS OF THIS FORMULA ARE OF USE IN COLOUR PHOTOGRAPHY. WHEN THE COMPOUNDS ARE PRESENT DURING THE COLOUR DEVELOPMENT OF SILVER HALIDE PHOTOGRAPHIC MATERIAL THEY CAUSE AN INCREASE IN DENSITY OF THE RESULTANT DYE IMAGE.

United States Patent 3,701,661 COLOR DEVELOPING WITH A 4-SULFO NAPHTHAMIDE BASE Boris Peter Brand, Bramhall, England, assignor to Ilford Limited, Ilford, Essex, England No Drawing. Filed Nov. 25, 1970, Ser. No. 92,927 Claims priority, application Great Britain, Nov. 26, 1969, 57,799/ 69 Int. Cl. G03c 7/00 US. Cl. 96--55 7 Claims ABSTRACT OF THE DISCLOSURE This application describes a compound of the formula:

C ONRzRs AOgH wherein R is selected from an alkyl, aralkyl, alkaryl, acyl and a substituted acyl group and R and R are each selected from a hydrogen atom and an alkyl, aralkyl, alkaryl, aryl and a substituted aryl group.

Compounds of this formula are of use in colour photography. When the compounds are present during the colour development of silver halide photographic material they cause an increase in density of the resultant dye image.

This invention relates to new chemical compounds, to their production and to their use in colour photography.

According to the present invention there is provided a compound of the general Formula I:

CONR R wherein R is an alkyl, aralkyl or alkaryl group or an acyl group which is optionally substituted and R and R are each hydrogen atoms or an alkyl, aralkyl or alkaryl group, or an aryl group which is optionally substituted. In the compounds which are of particular use in colour photography, as hereinafter described, it is preferred when R R or R is an alkyl, aralkyl or alkaryl group that the alkyl residue comprises not more than 18 carbon atoms. Examples of substituent groups which may be present in R when it is an acyl group or in R or R when either is an aryl group are hydroxy, alkoxy, halogen, nitrile, amino, substituted amino, sulphonic acid, esterified sulphonic acid, carboxy acid and esterified carboxy acid. The compounds of Formula I are closely related to certain cyan colour couplers of the a-naphthol type, the hydroxy group being substituted and there being a sulphonic acid group in the 4 or coupling position. Compounds of Formula :I are prepared from the known a-naphthol compounds which comprise a sulphonic acid group in the 4-position.

Therefore, according to another aspect of the present invention, there is provided a process for the production of a compound of Formula I which comprises reacting "Ice an aqueous alkaline solution of a compound of the general Formula II:

SO H

where R and R have the meanings previously assigned to them with a compound of the general formula R X where R, has the meaning previously assigned to it and X is an anion under continuously alkaline conditions and separating the compound of general Formula I so formed.

It has been found that when a compound of general Formula I is present when colour photographic material is colour developed an increase in the colour contrast of the final dye image or images is obtained and also an increase in the maximum colour photographic density is obtained, there being substantially no increase in colour fog.

Therefore according to this aspect of the present invention there is provided a process for the colour development of exposed photographic silver halide material which comprises developing the material by means of a colour developer in the presence of a colour coupler or couplers and a compound of the general Formula I.

The colour couplers may be of the substantive type, i.e. present initially in the colour photographic material or of the non-substantive type, i.e. present in the colour developing solution. In the former case usually more than one colour coupler is present during the development process while in the latter case usually only one colour coupler is present.

The compounds of general Formula I may be present in the colour developing solution or may be present initially in the colour photographic material in a layer thereof, for example in a silver halide layer.

According to another aspect of the present invention, therefore, there is provided colour photographic material which comprises in at least one layer thereof at least one compound of general Formula I.

When the colour photographic material comprises three light-sensitive silver halide emulsion layers each of which contain a substantive colour coupler there may be present in each of these three layers a compound of general Formula -I.

As hereinbefore stated the compound of Formula 'I may be present initially in the colour developing solution during the colour development process and according, therefore, to another aspect of the present invention there is provided a photographic colour developing solution which comprises a colour developing agent and at least one compound of Formula I.

In an alternative embodiment of this aspect of the present invention the compound of Formula -I may be caused to be present during the colour development process by being adsorbed on to color photographic material from a bath with which the colour photographic material is treated after exposure and before colour development, e.g. a prehardening bath.

According to this aspect of the present invention there is provided a colour photographic material treatment bath for use in treating colour photographic material after exposure thereof and before development thereof which comprises in an aqueous solution at least one compound of general Formula I.

When the compounds of Formula I are present during a colour development process the colour developed mate rial exhibits an increase in colour contrast and maximum photographic density over control material which has been developed in the absence of compounds of Formula I. There is virtually no increase in colour fog when compounds of Formula I are present during colour development. The increase in colour contrast and maximum photographic density are significant when normal development times are employed but they are particularly apparent when an extended colour development time is used. By use of the process of the present invention is is possible to lower the coating weight of the silver and/or colour couplers in the colour photographic material, thus achieving a saving in the use of expensive raw materials. Further it is possible to prepare thinner gelatino silver halide layers and to obtain the same colour density using such layers by use of the present invention. The use of thinner layers yields increased image sharpness.

The compounds of Formula I may be added to any type of colour photographic material such as negative, reversal or print materials. By increasing the concentration of the compound in the layers an enhanced effect is obtained, the upper limit being set by the physical properties of the compound and when the increased thickness of the layer due to the additive is greater than the decrease in thickness resulting from lower coating weights of silver and colour coupler in cases where layer thickness is important.

The compounds of the invention when incorporated in the photographic material itself may be conveniently added to the silver halide gelatin emulsion as an aqueous solution of the free acid or of its sodium or potassium salt, preferably before the addition of colour coupler. When added to colour developer baths a similar aqueous solution may be used.

Coupler A CHBO-QGOCHIC QNHQ The following examples will serve to illustrate the invention.

EXAMPLE I Preparation of Compound I (1-methoxy-4-sulpho-2- hexadecylnaphthamide) 164 g. of 1-hydroxy-4-sulpho-2-hexadecylnaphthamide, 3.4 l. of water and 40 ml. of 33% caustic liquor was added to a 5 l. 4-necked round bottomed flask fitted with a water condenser, a thermometer, a dropping funnel and a mechanical stirrer. The contents of the flask were stirred at C. until the colour coupler was completely in solution. The solution was then cooled to (l-10 C. and 128 ml. dimethyl sulphate was added at drop rate at this temperature with stirring. The contents of the flask was then allowed to warm to room temperature (20 C.) with stirring and was left stirring overnight at this temperature. During this time caustic liquor was added to keep the solution alkaline to Brilliant Yellow Paper. The solution was acidified with hydrochloric acid and exanhydrous MgSO and distilled under vacuum to dryness. The product was recrystallised using 4:1 ethyl acetate: glacial acetic acid and carbon screened with Carbon DYl. The product was dried overnight at 45 C. in a vacuum oven. Yield=86.8 g. (51.5% 'I h. Yield). M. Pt.-= 153 C.

Analysis by NMR and Infra Red Spectra showed that that product was 1-methoxy-4-sulpho-Z-hexadecylnaphthamide.

EXAMPLE II Preparation of Compound 2 (l-methoxy-4-sulpho-2N- octadecylamine naphthamide) 76 g. 2-(6-methyl-N-octadecylcarbamoyl)-4-sulpho-lnaphtho'l, 1 1. water and 18 ml. 33% caustic liquor was added to a 2 l. 4-necked round bottomed flask fitted with a water condenser, a thermometer, a dropping funnel and a mechanical stirrer. The contents of the flask were stirred at 40 C. until the colour coupler was completely in solution. The solution was then cooled to 0-10" C. and ml. of dimethyl sulphate was added at drop rate at this temperature with stirring. The contents of the flask were then allowed to warm to room temperature (20 C.) with stirring and were left stirring overnight at this temperature. During this time caustic liquor was added to keep the solution alkaline to Brilliant Yellow Paper. The solution was acidified with hydrochloric acid and extracted with butanol. 'Ihe butanol extract was dried over anhydrous Na SO and distilled under vacuum.

Yield=60 g. (76.8% 'Ih. Yield).

Examples III and IV which follow relate to the use of compounds I and II as just prepared in photographic colour processing.

In these examples the following colour couplers A, B, C, D and B were used COOH NHCOCHZCH COCH:

Coupler B N omQcoomo ONE O OH Coupler C O CH; omo-Qooomo ONH C 0 OH NHC OCH: Cfi Cia n C O C H (C H Coupler D CaH5-NN C O OH 0- NHC O CHaCE N C12H2s ('30 C H:

tracted with butanol. The butanol extract was dried over Coupler E SOaNa 1 Negative films were colour processed in colour developer I-C of the following composition:

Colour developer I-C G Sodium metaborate 53.3 Caustic soda 1.3 Sodium sulphite (anhydrous) 3.89 Potassium bromide 0.7 Hydroxylamine hydrochloride 1.98 Sodium sulphate 7.78

N,N-ethy1-w-hydroxybutyl p phenylene diamine sulphate Water to 1 l.

pH=10.4i0.1

Colour paper was processed in colour developer II-C of the following composition:

Colour developer I'I-C Calgon solution ml Sodium carbonate (anhydrous) g 60 Sodium sulphite (anhydrous) g 2 Potassium bromide g 0.5 Hydroxylamine hydrochloride g 2.0 p-Amino-N-ethyl-N-;8-hydroxy ethyl aniline sulphate g 4.5 Water to 1 l.

Substantive reversal film was processed in black and white developer I-B of the following composition:

Black and white developer I-B A-fter re-exposure the film was processed in the colour developer III-C of the following composition:

Colour developer III-C Trisodium phosphate g 80 Hydroxylamine sulphate g 2.4 Sodium sulphite (anhydrous) g 4.0 Potassium bromide g 1.0 p-Amino-N-ethyl-N-fi-hydroxy eth-yl aniline sulphate g 6.7 0.1% potassium iodide solution m'l 5.0 Water to 1 l.

pH=12.0- -0.l.

EXAMPLE III An aqueous solution of compound I was added to a negative emulsion at least 10 minutes before the addition of a methanolic alkaline solution of coupler A. HCl was added to the negative emulsion prior to the addition of compound I and coupler A so that the final pH was 6.0. The concentration of compound I, coupler A and silver in the coatings is given in Table 1 below.

Photographic data lor a development time 01- Coating details-coating weights, mg./dm.

Compound 4 6 8 10 12 I Coupler A Silver min. min. mm. min. min.

Contrast Maximum photographic density Contrast Maximum photographic density The results show that the addition of compound I gives an increase in contrast and maximum photographic density.

EXAMPLE IV An alkaline solution of compound I was added to a negative emulsion at least 10 minutes before the addition of a methanolic alkaline solution of coupler B. 1101 was added to the negative emulsion prior to the addition of compound I and coupler B so that the final pH was 6.0. The concentration of compound I, coupler B and silver in the coatings is given in Tab-1e 2 below. Colour development of sensitometrically exposed coatings using the colour developer I-C followed by bleaching and fixing to remove the silver gave the results shown in Table 2. Contrast was taken as the slope of the straight line portion of the characteristic curve.

The results show that the addition of compound I to coupler B gives an increase in contrast for development times 4 minutes and an increase in maximum photographic density for development times 2 minutes.

EXAMPLE V Example IV was repeated using coupler C instead of coupler B. The concentration of compound I, coupler C and silver in the coatings is given in Table 3 below. Colour development of sensitometrically exposed coatings using the colour developer I-C followed by bleach- 7 ing and fixingto remove the silver gave the results shown in Table 3.

TAB LE 3 Coating details- Photographic data for a coating weights, mgJdmJ development time of- Compound I Coupler C Silver 2 min. 3min. 4min. 5min. 6min Contrast Maximum photographic density The results show that the addition of compound I to coupler C gives an increase in contrast and maximum photographic density.

EXAMPLE VI Example IV was repeated using coupler D instead of coupler B. The concentration of compound I, coupler D and silver in the coatings is given in Table 4 below. Colour development of sensitometrically exposed coatings using the colour developer I-C followed by bleaching and fixing to remove the silver gave the results shown in Table 4.

TABLE 4 Coating details- Photographic data for a coating weights, mg./dm. development time of- Com- Coupound I pler D Silver 4 min. 6 min. 8 min.

Contrast Maximum photographic density The results show that the addition of compound I to coupler -D allows one to economise on the use of silver halide to obtain similar photographic characteristics.

EXAMPLE VII Example IV was repeated using compound 2 instead of compound I. The concentration of compound 2, coupler A and silver in the coatings is given in Table 5 below. Colour development of sensitometrically exposed coatings using the colour developer I-C followed by bleaching and fixing to remove the silver gave the following results.

The results show that the addition of compound 2 to coupler A gives an increase in contrast and maximum photopgraphic density.

EXAMPLE VIII An alkaline solution of compound I was added to a colour paper emulsion at least minutes before the addition of a 'methanolic alkaline solution of coupler A. HCl was added to the paper emulsion prior to the addition of compound I and coupler A so that the final pH was 6.0. The concentration of compound I, coupler A and silver in the coatings isv given in Table 6 below. Colour development of sensitometrically exposed coatings using the colour developer II-C followed by bleaching and fixing to remove the silver gave the following results.

TABLE 6 Photographic data for a development time of- Coating details-coating weights, mgJdm.

Com- Coupler 4 6 8 1O 12 16 pound I A Silver min. min. min. min. min. min.

Contrast Maximum photographic density The above results show that the addition of 1.66 mg./ dm. of compound I allows one to reduce the silver coating weight from 14.2 to 10.7 mg./dm. a saving of ca. 25% and the coupler coating weight from 8.8 to 6.6 mg./dm. -a saving of ca. 23

EXAMPLE 1X An alkaline solution of compound I was added to a negative emulsion at least 10 minutes before the addition of a methanolic alkaline solution of a colourless masking magenta coupler E. HCl was added to the negative emulsion prior to the addition of compound I and coupler B so that the final pH was 6.0. The concentration of compound I, coupler E and silver in the coatings is given in Table 7. Colour development of sensitometrically exposed coatings for the standard time (6 minutes) using the colour developer I-C gave the following results.

TABLE 7 Coating details-coating Photographic data weights, mgJdm.

Maximum Com- Coupler photographic pound I E Silver Contrast density Speed Speed was measured at 0.2 density above fog.

The results show that the addition of compound I to coupler E gives an increase in contrast, maximum photographic density and speed.

EXAMPLE X An alkaline solution of compound I was added to a photographic emulsion at least 10 minutes before the addition of a methanolic alkaline solution of coupler A. HCl was then added to the emulsion so that the final pH was 6.0. The concentration of compound I, coupler A and silver in the coatings is given in Table 8 below. Reversal colour development of sensitometrically exposed coatings using the black and white developer LB and the colour developer III-C followed by bleaching and fixing to remove the silver gave the following results.

TABLE 8 Photographic data for a development time of- Coating details-coating weights, mgJdmJ Com- Coupler poundI A Silver 2min. 4min. 6min. 8min. 10 min.

Contrast Maximum photographic density These results show that the addition of compound I to coupler A gives an increase in contrast and maximum photographic density.

I claim as my invention:

1. In a process for the colour development of exposed photographic silver halide material by developing said material by means of a colour developer in the presence of a colour coupler, the improvement which comprises performing the development in the presence of a compound of the formula:

pound of the formula: 20

wherein R and R are each alkyl of up to 18 carbon atoms and R is hydrogen or alkyl of up to 18 carbon atoms.

3. A multilayer colour photographic material which 35 comprises three light-sensitive silver halide layers each of which contain a substantive colour coupler and at least one compound of the formula:

CONRzR;

SOaH

wherein R and R are each alkyl of up to 18 carbon atoms and R is hydrogen or alkyl of up to 18 carbon atoms.

4. A colour development process according to claim 1 wherein said compound is 1-methoxy-4-sulpho-Z-hexadecylnaphthamide.

5. A colour development process according to claim 1 wherein said compound is 1-meth0xy-4-sulpho-2-N- methyl-N-octadecylaminenaphthamide.

6. A silver halide photographic material according to claim 2 wherein said compound is 1-methoxy-4-sulpho-2- hexadecylnaphthamide.

7. A silver halide photographic material according to claim 2 wherein said compound is 1-methoxy-4-sulpho-2- N-methyl-N-octadecylaminenaphthamide.

References Cited UNITED STATES PATENTS 4/ 1966* Schulte et al. 96-100 2/1963 Rauch et al 96-100 US. Cl. X.R. 96100 

